US4349605A - Flame retardant radiation curable polymeric compositions - Google Patents

Flame retardant radiation curable polymeric compositions Download PDF

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US4349605A
US4349605A US06/185,460 US18546080A US4349605A US 4349605 A US4349605 A US 4349605A US 18546080 A US18546080 A US 18546080A US 4349605 A US4349605 A US 4349605A
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ethylene
composition
silane
parts
copolymer
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US06/185,460
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James W. Biggs
Melvin F. Maringer
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Equistar Chemicals LP
Millennium Petrochemicals Inc
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National Destillers and Chemical Corp
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Assigned to NATIONAL DISTILLERS AND CHEMICAL CORPORATION, A CORP.OF VA. reassignment NATIONAL DISTILLERS AND CHEMICAL CORPORATION, A CORP.OF VA. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BIGGS JAMES W., MARINGER MELVIN F.
Priority to US06/185,460 priority Critical patent/US4349605A/en
Priority to IE2050/81A priority patent/IE51546B1/en
Priority to BR8105711A priority patent/BR8105711A/en
Priority to MX189040A priority patent/MX157682A/en
Priority to GB8127085A priority patent/GB2083480B/en
Priority to NO813049A priority patent/NO159533C/en
Priority to FR8116988A priority patent/FR2489831A1/en
Priority to IT23844/81A priority patent/IT1139954B/en
Priority to NLAANVRAGE8104161,A priority patent/NL189303C/en
Priority to BE0/205902A priority patent/BE890269A/en
Priority to JP56140439A priority patent/JPS5778438A/en
Priority to CA000385534A priority patent/CA1172784A/en
Priority to DE19813135749 priority patent/DE3135749A1/en
Publication of US4349605A publication Critical patent/US4349605A/en
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Assigned to EQUISTAR CHEMICALS, LP reassignment EQUISTAR CHEMICALS, LP ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MILLENNIUM PETROCHEMICALS, INC. [FORMERLY KNOWN AS QUANTUM CHEMICAL CORPORATION, WHICH WAS FORMERLY KNOWN AS NATIONAL DISTILLERS AND CHEMICAL CORPORATION]
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/294Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958Metal or metal compound in coating

Definitions

  • This invention relates to radiation crosslinkable polymeric compositions which exhibit moisture, heat and flame resistance and which are useful in producing insulated wire and cable as well as molded products. More particularly, it relates to a radiation crosslinkable ethylene-vinyl ester or acrylate copolymer composition having a radiation crosslinked tensile strength substantially equal to a chemically crosslinked copolymer composition of the same general composition.
  • Fire retarding polymeric compositions exhibiting, inter alia, improved moisture and heat resistance consisting essentially of an intimate mixture of at least one crosslinkable polymer containing as a major component an ethylenevinyl acetate copolymer, one or more silanes and one or more hydrated inorganic fillers have found wide acceptance in the wire and cable art.
  • Compositions such as these are disclosed in U.S. Pat. Nos. 3,832,326 and 3,922,442 of North et al. These patents disclose compositions which contain 80 to 400, preferably 125-140 weight parts of filler per 100 weight parts of polymer and 0.5 to 5.0 parts of silane per 100 parts of filler. No specific concentration range of lubricant is disclosed although 2 parts of calcium stearate per 100 parts of polymer are utilized in all of the fourteen compositions of the examples.
  • the prior art polymeric compositions of North et al. exhibit a unique combination, or balance, of improved physical and electrical properties together with a high degree of flame and fire retardance.
  • halogenated polymers such as polyvinyl chloride and chlorosulfonated polyethylene, thereby eliminating hydrogen chloride fumes; without carbon black, thereby permitting its use as colored insulations; without any flame retardant coatings such as are currently required, thereby eliminating an additional step in manufacturing operations when the compositions are used as, e.g., insulating compounds extruded onto a conductor; and without antimony trioxide, thereby eliminating a very expensive compound.
  • compositions find particular use as white (an inherent property) and colored uniinsulation compositions, which can be extruded over metal, e.g., copper or aluminum, conductors, to provide a single layer insulating and jacketing composition which is rated according to U.L. standards for 90° C. operation, and in some cases operation at temperatures as high as 125°, at up to 600 volts.
  • the insulating compositions of North et al. have found particular utility in the insulation of switchboard wire, appliance wire, and automotive wire where a unique combination of superior electrical properties combined with resistance to the degradative effects of heat and flame are essential, and where low smoke density and non-corrosive fumes are desirable.
  • North et al. prefer to crosslink the ethylenevinyl acetate copolymers in their compositions by irradiation with high energy sources or through the use of chemical crosslinking agents.
  • radiation cured compositions prepared in accordance with the disclosures of North et al. have poorer physical strength properties than their peroxide cured counterparts. The reasons for this are not fully understood although the precise nature and amount of the major and minor components in the composition are thought to be a contributing factor. Attempts to improve the physical strength of North et al.-type compositions have not met with appreciable success to date.
  • the physical strength of radiation cured ethylene copolymers (particularly ethylene-vinyl acetate copolymers) compositions containing silane-treated hydrated inorganic fillers can be significantly improved if (1) a lubricant composition comprising lauric acid and ethylene-bis-stearamide is substituted for the stearate lubricant employed heretofore and (2) the silane concentration is significantly increased over that employed heretofore. More particularly, this invention is directed to a radiation crosslinkable polymeric composition comprising:
  • the present invention may also be described as being concerned with the improvement in a radiation crosslinkable polymeric composition of the type containing:
  • the present invention relates to radiation crosslinkable polymeric compositions comprising copolymers of ethylene and a vinyl ester of an aliphatic carboxylic acid, an alkyl acrylate or an alkyl methacrylate and a silane-treated hydrated inorganic filler which exhibits significantly higher physical strength in its radiation crosslinked form than comparable radiation crosslinked compositions have exhibited heretofore. Further these radiation cured compositions have physical strength properties substantially similar to those of a comparable chemical crosslinked polymeric composition.
  • compositions of the present invention contain many of the components comprising the compositions disclosed in U.S. Pat. Nos. 3,832,326 and 3,922,442 of North et al., the disclosures of which are incorporated herein by reference.
  • crosslinkable or crosslinking are ascribed their normal art recognized meaning the present application, i.e., they denote the formation of primary valence bonds between polymer molecules.
  • compositions of the present invention are preferably crosslinked by radiation means.
  • the basic procedures for radiation crosslinking includes those using cobalt-60, accelerators, beta rays, gamma rays, X-rays, etc. These procedures for radiation crosslinking are extremely well known in the art and will not be described here in detail.
  • the polymeric component of the present composition is a copolymer of ethylene and a comonomer which may be a vinyl ester, an acrylate or a methacrylate.
  • the vinyl ester may be a vinyl ester of a C 2 -C 6 aliphatic carboxylic acid, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate or vinyl hexanoate.
  • the acrylates and methacrylates may be any of the C 1 -C 6 alkyl esters including, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl acrylate or methacrylate.
  • the preferred copolymer comprising the polymeric component of this invention is an ethylene-vinyl acetate copolymer containing about 9 to about 90%, preferably about 9 to about 40%, most preferably about 9 to about 28%, vinyl acetate, balance ethylene.
  • compositions of North et al. contained an ethylene-vinyl acetate copolymer as the preferred polymeric constituent
  • minor amounts of other crosslinkable polymers or copolymers could be included.
  • ethylene-vinyl acetate copolymer comprised at least 66% of the total polymers present in the North et al. compositions.
  • Representative of the minor polymeric components used in the non-preferred embodiments included polyethylene, copolymers of ethylene with propylene, butene, the acrylates and maleates, polydimethyl siloxane and polymethylphenylsiloxane, copolymers of vinyl acetate with the acrylates, etc. Obviously, mixtures of these minor polymeric components were also used.
  • Terpolymers of ethylene and vinyl acetate derived from, e.g., any of the corresponding monomeric materials listed above (other than ethylene or vinyl acetate) could also be used.
  • a representative terpolymer would be an ethylene-vinyl acetate-vinyl maleate terpolymer.
  • the ethylene-vinyl acetate copolymers used by North et al. preferably have a melt index of from about 1.0 to about 20.0.
  • the polyethylenes used in the North et al. composition include essentially all high, medium and low density polyethylenes as well as mixtures thereof.
  • the most preferred polyethylenes for blending for use as constitutional wires and cables generally have a density of from about 0.900 to about 0.950 gm./cc. and a melt index of from about 1.0 to about 10.0.
  • compositions of the present invention may also be used in the compositions of the present invention such is not preferred and in fact these non-preferred compositions do not provide the superior physical strength in the crosslinked composition that is obtained when a single copolymer, preferably an ethylene-vinyl acetate copolymer, is employed as the polymeric component.
  • compositions of the present invention provide a superior and unexpected balance of:
  • moisture resistance i.e., low mechanical absorption of water which yields a superior dielectric constant.
  • the present compositions are especially adapted for service as uniinsulation in the under 5000 volt, most especially in the under 600 volt range, where only a single extruded coating is used, and it is in the environment that a superior balance of properties is required. It has been further found that ethylene-vinyl acetate copolymers will hold very large amounts of filler and still provide high flexibility and a high degree of crosslinking. The simultaneous achievement of high filler loading, flexibility and crosslinking is quite surprising as high flexibility and high crosslinking are generally believed incompatible, as are high crosslinking and high filler loading (which implies low crosslinkable polymer content). Ethylene-vinyl acetate copolymers further provide superior fire retardance to the polymeric compositions of the present invention.
  • silane may be used in the present invention which will not adversely affect the desired balance of properties and which will help to bind the polymer and inorganic filler of the present invention, provided that the silane is not combustible, e.g., alkoxy and amine silanes, and does not interfere with polymer crosslinking or degrade during polymer processing.
  • the preferred silanes used in forming the insulating compositions are the alkoxy silanes, e.g., lower alkyl-, alkenyl-, alkynl- and aryl-alkoxysilanes as well as the lower alkyl-, alkenyl-, alkynl- and aryl-alkoxyalkoxy or -aryloxy alkoxy silanes.
  • alkoxy silanes e.g., lower alkyl-, alkenyl-, alkynl- and aryl-alkoxysilanes as well as the lower alkyl-, alkenyl-, alkynl- and aryl-alkoxyalkoxy or -aryloxy alkoxy silanes.
  • silanes are methyltriethoxy-, methyltris(2 methoxyethoxy)-, dimethyldiethoxy-, alkyltrimethoxy-, vinyltris(2-methoxyethoxy)-, phenyl-tris(2-methoxyethoxy)-, vinyltrimethoxy- and vinyltriethoxy-silane.
  • vinyl silanes it is preferred to use the vinyl silanes for best results, and of the vinyl silanes the following are especially preferred:
  • H 2 C CHSi(OCH 2 CH 2 OCH 3 ) 3
  • the fillers used in the present invention are the hydrated inorganic fillers, e.g., hydrated aluminum oxides (Al 2 O 3 .3H 2 O or Al(OH) 3 ), hydrated magnesia, hydrated calcium silicate. Of these compounds, the most preferred is hydrated aluminum oxide.
  • a hydrated inorganic filler be used in formulating the polymeric compositions. It must be emphasized that large proportions of another type of filler, be it inert or not, cannot be added to the compositions and still achieve the superior balance of properties.
  • the water of hydration in the inorganic filler must be released during the application of heat sufficient to cause combustion or ignition of the ethylene-vinyl acetate copolymer.
  • the water of hydration chemically bound to the inorganic filler is released endothermically. It has been found that the hydrated inorganic filler increased flame retardance in a manner far superior to other fillers previously used by the art to provide insulation with flame retardance e.g., carbon black, clays, titanium dioxide, etc. What is even more surprising is that flame retardance is combined with excellent electrical insulation properties at the high filler loadings used, since at these loadings the copolymeric composition contains a large amount of bound water.
  • the filler size should be in accordance with those sizes used by the prior art.
  • a lubricant form a portion of the insulating composition.
  • Such lubricants as a fatty acid soap or a metallic derivative thereof have been used heretofore.
  • the lubricant not only aids in the extrusion process but it also improves the stripping properties of wire insulation thereby facilitating the task of the end-user.
  • the lubricant component comprises an essential component of the polymeric compositions of this invention. It has been found that the combination of a preferred silane in the required concentration plus a particular two component lubricant composition provided in a lubricating effective amount unexpectedly improves the physical strength of the radiation crosslinked compositions of the present invention.
  • Calcium stearate has often been employed heretofore as a lubricant for polymeric compostions such as those of North et al. Generally, those which were radiation crosslinked exhibited a tensile strength substantially lower than the chemically crosslinked counterpart. It was found that the physical strength properties of the radiation cured compositions could be improved somewhat if an aluminum stearate replaced the calcium stearate but the physical properties were still less than those of the chemically cured calcium stearate composition.
  • a lubricant composition comprising lauric acid and ethylene-bis-stearamide when used in combination with an appropriate quantity of a preferred silane will produce a radiation cured composition with significantly enhanced physical strength properties.
  • the lubricant composition employed in the composition of the present invention is composed of 15-35% lauric acid and 85-65% ethylene-bis-stearamide.
  • One particularly preferred lubricant contains about 25% lauric acid and about 75% ethylene-bis-stearamide and is available commercially under the tradename Mold-Wiz.
  • the amounts of polymer and filler can be varied within wide proportions. Best results are obtained in coating, e.g., extruding, onto electrical wire and cables when from 80 to 400 parts of filler, preferably 100-135 parts of filler, per 100 parts of polymer are employed. All percentages and parts referred to herein are by weight, unless otherwise indicated.
  • silane and the composition of the lubricant which are essential to the improved tensile strength obtained when the compositions of this invention are radiation crosslinked.
  • the useful amounts of silane are from 2 to 8 parts or higher, preferably from 2.5 to 6 parts, of silane per 100 parts of hydrated filler.
  • the required amount of silane is employed in combination with a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide.
  • a lubricating effective amount is generally in the range of 0.5 to 5 parts of lubricant per 100 parts of resin.
  • compositions of the present invention may be formed in a number of ways.
  • the preferred method of filler treatment is by direct addition of the silane to the polymer followed by addition thereto of the filler, the lubricant, and other additives, if desired. This can be done in an internal mixer, such as Banbury or Werner & Pfleiderer mixer.
  • the silane may be added directly to the filler, dispersed therein, and the polymer and lubricant then added.
  • any processing device known to the art which insures an intimate mixture of all three essential components may be used, provided the silane is intimately and thoroughly dispersed onto the surface of the hydrated inorganic filler.
  • Aluminum stearate which provides superior physical properties to radiation cured composition as compared to the calcium stearate employed in the chemically cured composition, was evaluated against a lubricant composed of lauric acid and ethylene-bis-stearamide. The latter was a mixture of 25% lauric acid--75% ethylene-bis-stearamide available under the trade name Mold-Wiz 33 UDK.
  • alkoxy silane and a lubricant of lauric acid and ethylene-bis-stearamide was evaluated on a coated wire at a 12.5 MR radiation cure and evaluated against comparative compositions, one of which was peroxide cured and the other was radiation cured.
  • the sample of the present invention had the following composition:
  • the comparative radiation-curable composition had the following composition:
  • the peroxide curable composition was similar to the comparative radiation curable composition but contained, in addition, an organic peroxide.

Abstract

Radiation crosslinked compositions containing copolymers of ethylene and a vinyl ester or an acrylate, a hydrated inorganic filler, a higher concentration of silane than employed heretofore and a lubricant of lauric acid and ethylene-bis-stearamide exhibit physical strength properties substantially similar to a chemically crosslinked counterpart.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to radiation crosslinkable polymeric compositions which exhibit moisture, heat and flame resistance and which are useful in producing insulated wire and cable as well as molded products. More particularly, it relates to a radiation crosslinkable ethylene-vinyl ester or acrylate copolymer composition having a radiation crosslinked tensile strength substantially equal to a chemically crosslinked copolymer composition of the same general composition.
2. Description of the Prior Art
One of the most important areas where fire resistant polymer compositions find use is in the electrical environment, i.e., where both insulating and fire resistant properties are sought, most especially in the area of conductor insulation. At one time, extrudable compositions available to the wire and cable art were required, for flame resistance, to contain halogenated polymers such as chlorinated polyethylene, polyvinyl chloride, chlorobutadiene, chlorinated paraffin, etc., together with antimony trioxide, both components being present in sizable quantities. Alternatively, a coating of chlorosulfonated polyethylene paint was applied to a nonflame retardant insulating compound which constituted an additional manufacturing operation.
For certain types of dry transformers, particularly high voltage transformers, a problem existed in that electrical failures occurred due to surface creepage of the organic insulating component used. The problem was solved through the addition of hydrated alumina to compositions whose organic binder consisted of butyl rubber, epoxy resins or polyester resins. However, these compositions do not possess a balance of excellent extrudability characteristics, physical and electrical properties, heat resistance and flame retardance. Such compositions are disclosed in U.S. Pat. Nos. 2,997,526-7 and 8 of Kessel et al. The described compositions for such usage have poor tensile strength, elongation and percent elongation retained after aging.
Fire retarding polymeric compositions exhibiting, inter alia, improved moisture and heat resistance consisting essentially of an intimate mixture of at least one crosslinkable polymer containing as a major component an ethylenevinyl acetate copolymer, one or more silanes and one or more hydrated inorganic fillers have found wide acceptance in the wire and cable art. Compositions such as these are disclosed in U.S. Pat. Nos. 3,832,326 and 3,922,442 of North et al. These patents disclose compositions which contain 80 to 400, preferably 125-140 weight parts of filler per 100 weight parts of polymer and 0.5 to 5.0 parts of silane per 100 parts of filler. No specific concentration range of lubricant is disclosed although 2 parts of calcium stearate per 100 parts of polymer are utilized in all of the fourteen compositions of the examples.
The prior art polymeric compositions of North et al. exhibit a unique combination, or balance, of improved physical and electrical properties together with a high degree of flame and fire retardance. These highly desirable results are achieved without the use of halogenated polymers such as polyvinyl chloride and chlorosulfonated polyethylene, thereby eliminating hydrogen chloride fumes; without carbon black, thereby permitting its use as colored insulations; without any flame retardant coatings such as are currently required, thereby eliminating an additional step in manufacturing operations when the compositions are used as, e.g., insulating compounds extruded onto a conductor; and without antimony trioxide, thereby eliminating a very expensive compound.
Such compositions find particular use as white (an inherent property) and colored uniinsulation compositions, which can be extruded over metal, e.g., copper or aluminum, conductors, to provide a single layer insulating and jacketing composition which is rated according to U.L. standards for 90° C. operation, and in some cases operation at temperatures as high as 125°, at up to 600 volts.
The insulating compositions of North et al. have found particular utility in the insulation of switchboard wire, appliance wire, and automotive wire where a unique combination of superior electrical properties combined with resistance to the degradative effects of heat and flame are essential, and where low smoke density and non-corrosive fumes are desirable.
North et al. prefer to crosslink the ethylenevinyl acetate copolymers in their compositions by irradiation with high energy sources or through the use of chemical crosslinking agents. As has been observed with other radiation cured polymeric compositions, radiation cured compositions prepared in accordance with the disclosures of North et al. have poorer physical strength properties than their peroxide cured counterparts. The reasons for this are not fully understood although the precise nature and amount of the major and minor components in the composition are thought to be a contributing factor. Attempts to improve the physical strength of North et al.-type compositions have not met with appreciable success to date.
Two North et al.-type crosslinkable polymeric compositions as shown in the examples, particularly Example II, demonstrate this difference. One product is peroxide curable while the other is radiation curable. Several modifications were made to the peroxide curable product to produce the radiation curable counterpart. The copolymer in the radiation curable product has a higher vinyl acetate content and aluminum stearate has been substituted for the calcium stearate lubricant. Although this has improved the physical strength of the radiation cured composition over what it would have been, it is still significantly lower than the peroxide cured product.
It is an object of this invention to provide a radiation crosslinkable ethylene copolymer composition having physical strength properties in its crosslinked state which are superior to those obtained heretofore.
It is another object of this invention to provide a radiation crosslinkable ethylene copolymer composition which not only exhibits superior moisture, heat and flame resistance but also possesses superior physical strength when it is crosslinked than has been obtained heretofore.
SUMMARY OF THE INVENTION
In accordance with the present invention, it has been found that the physical strength of radiation cured ethylene copolymers (particularly ethylene-vinyl acetate copolymers) compositions containing silane-treated hydrated inorganic fillers can be significantly improved if (1) a lubricant composition comprising lauric acid and ethylene-bis-stearamide is substituted for the stearate lubricant employed heretofore and (2) the silane concentration is significantly increased over that employed heretofore. More particularly, this invention is directed to a radiation crosslinkable polymeric composition comprising:
(a) a copolymer of ethylene and a vinyl ester of a C2 -C6 aliphatic carboxylic acid, a C1 -C6 alkyl acrylate or C1 -C6 alkyl methacrylate,
(b) from 80 to 400 parts of hydrated inorganic filler per 100 parts of copolymer,
(c) 2.5 to 6 parts of an alkoxy silane per 100 parts of hydrated inorganic filler, and
(d) a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide.
The present invention may also be described as being concerned with the improvement in a radiation crosslinkable polymeric composition of the type containing:
(a) a copolymer of ethylene and a vinyl ester of a C2 -C6 aliphatic carboxylic acid, a C1 -C6 alkyl acrylate or a C1 -C6 alkyl methacrylate, and
(b) a silane-treated hydrated inorganic filler, the concentration of said filler being 80 to 400 parts of filler per 100 parts of copolymer,
which comprises utilizing as the silane, an alkoxysilane in the amount of 2.5 to 6 parts per 100 parts of filler and incorporating in said composition a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide.
This invention also relates to an electrical conductor coated with a uniinsulating layer comprising these crosslinkable polymeric compositions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to radiation crosslinkable polymeric compositions comprising copolymers of ethylene and a vinyl ester of an aliphatic carboxylic acid, an alkyl acrylate or an alkyl methacrylate and a silane-treated hydrated inorganic filler which exhibits significantly higher physical strength in its radiation crosslinked form than comparable radiation crosslinked compositions have exhibited heretofore. Further these radiation cured compositions have physical strength properties substantially similar to those of a comparable chemical crosslinked polymeric composition.
The compositions of the present invention contain many of the components comprising the compositions disclosed in U.S. Pat. Nos. 3,832,326 and 3,922,442 of North et al., the disclosures of which are incorporated herein by reference.
The Crosslinkable Copolymer Components
The terms crosslinkable or crosslinking are ascribed their normal art recognized meaning the present application, i.e., they denote the formation of primary valence bonds between polymer molecules.
Although crosslinking of polymers can be achieved by such known procedures as chemical crosslinking, thermal crosslinking or radiation crosslinking, the compositions of the present invention are preferably crosslinked by radiation means. The basic procedures for radiation crosslinking includes those using cobalt-60, accelerators, beta rays, gamma rays, X-rays, etc. These procedures for radiation crosslinking are extremely well known in the art and will not be described here in detail.
The polymeric component of the present composition is a copolymer of ethylene and a comonomer which may be a vinyl ester, an acrylate or a methacrylate. The vinyl ester may be a vinyl ester of a C2 -C6 aliphatic carboxylic acid, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate or vinyl hexanoate. The acrylates and methacrylates may be any of the C1 -C6 alkyl esters including, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl acrylate or methacrylate. The preferred copolymer comprising the polymeric component of this invention is an ethylene-vinyl acetate copolymer containing about 9 to about 90%, preferably about 9 to about 40%, most preferably about 9 to about 28%, vinyl acetate, balance ethylene.
Although the prior art compositions of North et al., of which the present compositions are an improvement, contained an ethylene-vinyl acetate copolymer as the preferred polymeric constituent, minor amounts of other crosslinkable polymers or copolymers could be included. However, ethylene-vinyl acetate copolymer comprised at least 66% of the total polymers present in the North et al. compositions. Representative of the minor polymeric components used in the non-preferred embodiments included polyethylene, copolymers of ethylene with propylene, butene, the acrylates and maleates, polydimethyl siloxane and polymethylphenylsiloxane, copolymers of vinyl acetate with the acrylates, etc. Obviously, mixtures of these minor polymeric components were also used.
Terpolymers of ethylene and vinyl acetate derived from, e.g., any of the corresponding monomeric materials listed above (other than ethylene or vinyl acetate) could also be used. A representative terpolymer would be an ethylene-vinyl acetate-vinyl maleate terpolymer.
The ethylene-vinyl acetate copolymers used by North et al. preferably have a melt index of from about 1.0 to about 20.0.
The polyethylenes used in the North et al. composition include essentially all high, medium and low density polyethylenes as well as mixtures thereof. The most preferred polyethylenes for blending for use as uniisulation for electrical wires and cables generally have a density of from about 0.900 to about 0.950 gm./cc. and a melt index of from about 1.0 to about 10.0.
Although minor amounts of the polymers and copolymers employed in minor proportions by North et al. may also be used in the compositions of the present invention such is not preferred and in fact these non-preferred compositions do not provide the superior physical strength in the crosslinked composition that is obtained when a single copolymer, preferably an ethylene-vinyl acetate copolymer, is employed as the polymeric component.
As is true with the North et al. prior art compositions, the compositions of the present invention provide a superior and unexpected balance of:
1. low temperature brittleness, i.e., the composition will not readily crack during low temperature movement (ASTM D 746).
2. heat resistance after aging, i.e., excellent elongation after extended service at 90° C. and even 125° C.
3. arcing and tracking resistance, as high as 5 KV, whereas even porcelain shows surface breakdown at 4 KV. This property is not often required, however, in the preferred environment of under 600 volt service.
4. flame resistant and flame retardance.
5. moisture resistance, i.e., low mechanical absorption of water which yields a superior dielectric constant.
6. resistance to industrial chemicals.
In addition, when these compositions are radiation crosslinked they exhibit tensile strengths superior to the radiation crosslinked compositions of the prior art and substantially equal to that of the chemically crosslinked prior art compositions.
It is not known why the compositions of this invention provide such a superior balance of properties. It is possible to theorize that there is some synergistic relationship between the ethylene copolymer, silane, hydrated inorganic filler, and the preferred lubricant, but there is no intention to be bound by such a theory. However, it has been established that for low voltage environments, less than 5000 volts, even more particularly for less than 600 volt environments, the compositions of this invention are equal to the prior art for service as uniinsulation. Uniinsulation is an art accepted term denoting insulation where one layer is extruded around the conductor, and this one layer serves as the electrical insulation and the jacketing to provide physical and flame protection. The present compositions are especially adapted for service as uniinsulation in the under 5000 volt, most especially in the under 600 volt range, where only a single extruded coating is used, and it is in the environment that a superior balance of properties is required. It has been further found that ethylene-vinyl acetate copolymers will hold very large amounts of filler and still provide high flexibility and a high degree of crosslinking. The simultaneous achievement of high filler loading, flexibility and crosslinking is quite surprising as high flexibility and high crosslinking are generally believed incompatible, as are high crosslinking and high filler loading (which implies low crosslinkable polymer content). Ethylene-vinyl acetate copolymers further provide superior fire retardance to the polymeric compositions of the present invention.
The above described ethylene copolymers are crosslinked by irradiation with high-energy electron beams. Fully crosslinked, these polymers become thermoset in behavior.
The art of radiation crosslinking is so highly developed that little need be said with respect to such procedures. As higher total doses of radiation are used, the degree of crosslinking generally increases, and for preferred crosslinkings a total radiation dose of about 5-25 megarads will be used.
In general, the higher the degree of crosslinking the more resistant the polymeric composition is to moisture, chemical reagents, etc., and the less resistant the polymeric composition is to abrasion. At lower degrees of crosslinking there is also some loss of heat resistance as well as pronounced effect on percent elongation after aging. The exact degree of crosslinking can, of course, be varied to take the above factors and their effect on the final product into account.
The Silane Component
One or more substituted silanes comprise the second essential component of the polymeric compositions of the present invention.
Any silane may be used in the present invention which will not adversely affect the desired balance of properties and which will help to bind the polymer and inorganic filler of the present invention, provided that the silane is not combustible, e.g., alkoxy and amine silanes, and does not interfere with polymer crosslinking or degrade during polymer processing.
The preferred silanes used in forming the insulating compositions are the alkoxy silanes, e.g., lower alkyl-, alkenyl-, alkynl- and aryl-alkoxysilanes as well as the lower alkyl-, alkenyl-, alkynl- and aryl-alkoxyalkoxy or -aryloxy alkoxy silanes. Specific examples of such silanes are methyltriethoxy-, methyltris(2 methoxyethoxy)-, dimethyldiethoxy-, alkyltrimethoxy-, vinyltris(2-methoxyethoxy)-, phenyl-tris(2-methoxyethoxy)-, vinyltrimethoxy- and vinyltriethoxy-silane.
It is preferred to use the vinyl silanes for best results, and of the vinyl silanes the following are especially preferred:
gamma-Methacryloxypropyltrimethoxy-Silane ##STR1## and Vinyl-Tris(2-Methoxyethoxy)Silane
H2 C=CHSi(OCH2 CH2 OCH3)3
The Hydrated Inorganic Filler Component
The fillers used in the present invention are the hydrated inorganic fillers, e.g., hydrated aluminum oxides (Al2 O3.3H2 O or Al(OH)3), hydrated magnesia, hydrated calcium silicate. Of these compounds, the most preferred is hydrated aluminum oxide.
To obtain the superior balance of properties described, it is mandatory that a hydrated inorganic filler be used in formulating the polymeric compositions. It must be emphasized that large proportions of another type of filler, be it inert or not, cannot be added to the compositions and still achieve the superior balance of properties.
The water of hydration in the inorganic filler must be released during the application of heat sufficient to cause combustion or ignition of the ethylene-vinyl acetate copolymer. The water of hydration chemically bound to the inorganic filler is released endothermically. It has been found that the hydrated inorganic filler increased flame retardance in a manner far superior to other fillers previously used by the art to provide insulation with flame retardance e.g., carbon black, clays, titanium dioxide, etc. What is even more surprising is that flame retardance is combined with excellent electrical insulation properties at the high filler loadings used, since at these loadings the copolymeric composition contains a large amount of bound water.
The filler size should be in accordance with those sizes used by the prior art.
The Lubricant Component
When polymeric insulation is formed on conductors by extrusion, it is preferred that a lubricant form a portion of the insulating composition. Such lubricants as a fatty acid soap or a metallic derivative thereof have been used heretofore. The lubricant not only aids in the extrusion process but it also improves the stripping properties of wire insulation thereby facilitating the task of the end-user.
The lubricant component comprises an essential component of the polymeric compositions of this invention. It has been found that the combination of a preferred silane in the required concentration plus a particular two component lubricant composition provided in a lubricating effective amount unexpectedly improves the physical strength of the radiation crosslinked compositions of the present invention.
Calcium stearate has often been employed heretofore as a lubricant for polymeric compostions such as those of North et al. Generally, those which were radiation crosslinked exhibited a tensile strength substantially lower than the chemically crosslinked counterpart. It was found that the physical strength properties of the radiation cured compositions could be improved somewhat if an aluminum stearate replaced the calcium stearate but the physical properties were still less than those of the chemically cured calcium stearate composition.
It has been found, and this is an essential part of the present invention, that a lubricant composition comprising lauric acid and ethylene-bis-stearamide when used in combination with an appropriate quantity of a preferred silane will produce a radiation cured composition with significantly enhanced physical strength properties. The lubricant composition employed in the composition of the present invention is composed of 15-35% lauric acid and 85-65% ethylene-bis-stearamide. One particularly preferred lubricant contains about 25% lauric acid and about 75% ethylene-bis-stearamide and is available commercially under the tradename Mold-Wiz.
The Proportions of the Components
The amounts of polymer and filler can be varied within wide proportions. Best results are obtained in coating, e.g., extruding, onto electrical wire and cables when from 80 to 400 parts of filler, preferably 100-135 parts of filler, per 100 parts of polymer are employed. All percentages and parts referred to herein are by weight, unless otherwise indicated.
As discussed hereinbefore it is the quantity of the silane and the composition of the lubricant which are essential to the improved tensile strength obtained when the compositions of this invention are radiation crosslinked. The useful amounts of silane are from 2 to 8 parts or higher, preferably from 2.5 to 6 parts, of silane per 100 parts of hydrated filler. The required amount of silane is employed in combination with a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide. A lubricating effective amount is generally in the range of 0.5 to 5 parts of lubricant per 100 parts of resin.
The compositions of the present invention may be formed in a number of ways. For instance, the preferred method of filler treatment is by direct addition of the silane to the polymer followed by addition thereto of the filler, the lubricant, and other additives, if desired. This can be done in an internal mixer, such as Banbury or Werner & Pfleiderer mixer. Alternatively, the silane may be added directly to the filler, dispersed therein, and the polymer and lubricant then added.
Any processing device known to the art which insures an intimate mixture of all three essential components may be used, provided the silane is intimately and thoroughly dispersed onto the surface of the hydrated inorganic filler.
It will be apparent that in addition to the essential components of the compositions of this invention, other additives may be present, e.g., pigments, stabilizers, antioxidants (e.g., polymerized trimethyldihydro quinoline) so long as they do not interfere with crosslinking, when desired, or harm desired properties. Such materials are present in very minor proportions, ranging from less than 10% of the polymer, and usually in amounts of less than 5%. There are two reasons amounts of other components are not desirable: firstly, the present composition per se has such superior properties; secondly, any significant amounts of other fillers for example, serve only to degrade or upset the balance of properties.
The following examples will serve to illustrate the subject invention.
The same general procedure was employed in preparing each sample. In each instance the silane under evaluation, the hydrated alumina (Al2 O3.3H2 O), the lubricant being evaluated and an antioxidant (polymerized 1,2-dihydro-2,2,4-trimethyl-quinoline, in all instances) were added to the polymeric component and blended therewith. Following mixing, depending on the testing evaluation employed, the polymer composition was either formed into test plaques and radiation cured or extruded onto a copper wire using a Brabender extruder and radiation cured.
EXAMPLE I
Several lubricants were evaluated. Aluminum stearate, which provides superior physical properties to radiation cured composition as compared to the calcium stearate employed in the chemically cured composition, was evaluated against a lubricant composed of lauric acid and ethylene-bis-stearamide. The latter was a mixture of 25% lauric acid--75% ethylene-bis-stearamide available under the trade name Mold-Wiz 33 UDK.
The remaining components were:
______________________________________                                    
EVA copolymer (28% VA)                                                    
Hydrated alumina       118    phr                                         
Gamma-Methacryloxypropyl-                                                 
trimethoxy silane      3      phr                                         
Antioxidant            1      phr                                         
______________________________________                                    
The test results are presented in Table I below.
              TABLE I                                                     
______________________________________                                    
EFFECT OF MOLD WIZ VS. ALUMINUM STEARATE                                  
                         1 phr                                            
               2 phr     Mold Wiz                                         
               Al. Stearate                                               
                         33UDK                                            
______________________________________                                    
0 MR Cure                                                                 
Tensile, psi     1590        1600                                         
Elong., %        620         630                                          
H.sub.2 O Absorp. mg/in.sup.2                                             
                 46.1        35.4                                         
(7 days @ 82° C.)                                                  
10 MR Cure                                                                
Tensile, psi     1990        2320                                         
Elong., %        250         220                                          
Swell Ratio/Extract. %                                                    
                 4.45/9.72   4.37/7.77                                    
12.5 MR Cure                                                              
Tensile, psi     2110        2400                                         
Elong., %        240         200                                          
H.sub.2 O Absorp. mg/in.sup.2                                             
                 22.0        13.1                                         
Swell Ratio/Extract. %                                                    
                 4.38/8.12    3.6/5.69                                    
15 MR Cure                                                                
Tensile, psi     2120        2410                                         
Elong., %        210         190                                          
Swell Ratio/Extract. %                                                    
                 4.01/6.52   3.28/3.99                                    
17.5 MR Cure                                                              
Tensile, psi     1950        2220                                         
Elong., %        200         170                                          
H.sub.2 O Absorp. mg/in.sup.2                                             
                 15.3        12.0                                         
(7 days @ 82° C.)                                                  
Swell Ratio/Extract. %                                                    
                 4.03/7.15   3.36/5.60                                    
______________________________________                                    
These data show that a significant increase in tensile strength is realized if aluminum stearate is replaced with a lubricant of lauric acid and ethylene-bis-stearamide in radiation cured alumina-filled EVA compositions. In addition, the use of this two-component lubricant composition also provided decreased water absorption.
EXAMPLE II
The preferred combination of alkoxy silane and a lubricant of lauric acid and ethylene-bis-stearamide was evaluated on a coated wire at a 12.5 MR radiation cure and evaluated against comparative compositions, one of which was peroxide cured and the other was radiation cured.
The sample of the present invention had the following composition:
______________________________________                                    
EVA copolymer (28% VA)                                                    
Hydrated alumina       118    phr                                         
Vinyl tris (methoxyethoxy)                                                
silane                 3      phr                                         
Lubricant - 25% lauric acid/                                              
75% ethylene-bis-stearamide                                               
                       1      phr                                         
Polymerized 1, 2-dihydro-2,                                               
2, 4-trimethyl quinoline                                                  
                       1      phr                                         
______________________________________                                    
The comparative radiation-curable composition had the following composition:
______________________________________                                    
EVA copolymer (28% VA)                                                    
Hydrated alumina       118    phr                                         
Vinyl tris (methoxyethoxy)                                                
silane                 1      phr                                         
Lubricant - aluminum stearate                                             
                       2      phr                                         
Polymerized 1, 2-dihydro-2-,                                              
2, 4-trimethyl quinoline                                                  
                       1      phr                                         
______________________________________                                    
The peroxide curable composition was similar to the comparative radiation curable composition but contained, in addition, an organic peroxide.
The evaluation of wire coated with these compositions is present in Table II below.
              TABLE II                                                    
______________________________________                                    
                     Compar-   Compar-                                    
               Sub-  ative     ative                                      
               ject  Product   Product                                    
               Inven-                                                     
                     Radiation-                                           
                               Peroxide-                                  
               tion  Cured     Cured                                      
______________________________________                                    
Unaged                                                                    
Tensile Strength, psi                                                     
                 2350    1380      2390                                   
Elongation, %     260     210       250                                   
Aged 7 days at 158° C.                                             
Tensile Strength, psi                                                     
                 2910    1630      2670                                   
Elongation, %     190     220       210                                   
Aged 14 days at 158° C.                                            
Tensile Strength, psi                                                     
                 2740    --        2670                                   
Elongation, %     190    --         200                                   
Horizontal Flame Appl. Wire                                               
                 Pass    Pass      Pass                                   
______________________________________                                    
These data show that increasing the silane level and substituting a lauric acid/ethylene-bis-stearamide lubricant for aluminum stearate provides a radiation cured composition with improved dispersion and improved physical properties. In fact the physical properties of the improved radiation cured composition are comparable to a peroxide crosslinked counterpart.

Claims (15)

What is claimed is:
1. A radiation crosslinkable polymeric composition comprising:
(a) a copolymer of ethylene and a vinyl ester of a C2 -C6 aliphatic carboxylic acid, a C1 -C6 alkyl acrylate or a C1 -C6 alkyl methacrylate,
(b) from 80 to 400 parts of hydrated inorganic filler per 100 parts of copolymer,
(c) 2 to 8 parts of an alkoxy silane per 100 parts of hydrated inorganic filler, and
(d) a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide.
2. A composition according to claim 1 wherein the copolymer is an ethylene-vinyl acetate copolymer.
3. A composition according to claim 1 containing in addition:
(e) an antioxidizing effective amount of polymerized 1,2-dihydro-2,2,4-trimethyl-quinoline.
4. A composition according to claim 1 wherein the composition is radiation crosslinked.
5. A composition according to claim 1 wherein the silane is vinyl-tris(2-methoxyethoxy)silane or gamma-methacryloxypropyltrimethoxysilane.
6. A composition according to claim 1 wherein the filler is alumina.
7. A composition according to claim 1 wherein the lubricant comprises 15-35% lauric acid and 85-65% ethylene-bis-stearamide.
8. In a radiation crosslinkable polymeric composition of the type containing:
(a) a copolymer of ethylene and a vinyl ester of a C2 -C6 aliphatic carboxylic acid, a C1 -C6 alkyl acrylate or a C1 -C6 alkyl methacrylate, and
(b) a silane-treated hydrated inorganic filler, the concentration of said filler being 80 to 400 parts of filler per 100 parts of copolymer,
the improvement which comprises utilizing as the silane, an alkoxy silane in the amount of 2 to 8 parts per 100 parts of filler and incorporating in said composition a lubricating effective amount of a lubricant comprising lauric acid and ethylene-bis-stearamide.
9. The improvement according to claim 8 wherein the copolymer is an ethylene-vinyl acetate copolymer.
10. The improvement according to claim 8 wherein the composition additionally contains an antioxidizing effective amount of polymerized 1,2-dihydro-2,2,4-trimethyl-quinoline.
11. The improvement according to claim 8 wherein the composition is radiation crosslinked.
12. The improvement according to claim 8 wherein the silane is vinyl-tris(2-methoxyethoxy)silane or gamma-methacryloxypropyltrimethoxysilane.
13. The improvement according to claim 8 wherein the filler is alumina.
14. The improvement according to claim 8 wherein the lubricant comprises 15-35% lauric acid and 85-65% ethylene-bis-stearamide.
15. An electrical conductor coated with a uniinsulating layer comprising the radiation crosslinkable polymeric composition of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
US06/185,460 1980-09-09 1980-09-09 Flame retardant radiation curable polymeric compositions Expired - Lifetime US4349605A (en)

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US06/185,460 US4349605A (en) 1980-09-09 1980-09-09 Flame retardant radiation curable polymeric compositions
IE2050/81A IE51546B1 (en) 1980-09-09 1981-09-04 Flame retardant,radiation curable polymeric compositions
BR8105711A BR8105711A (en) 1980-09-09 1981-09-04 RADIATION-RETICULABLE POLYMERIC COMPOSITION
MX189040A MX157682A (en) 1980-09-09 1981-09-04 POLYMERIC COMPOSITIONS RADIO CURABLE CURRENT PIRORETARDANTS
NLAANVRAGE8104161,A NL189303C (en) 1980-09-09 1981-09-08 Radiation-crosslinkable polymeric compositions and method of radiation-crosslinking.
NO813049A NO159533C (en) 1980-09-09 1981-09-08 IRRAVABLE, FLAMMABLE POLYMER MATERIAL AND ITS USE FOR ISOLATING AN ELECTRIC WIRE.
FR8116988A FR2489831A1 (en) 1980-09-09 1981-09-08 IRRADIATION-CURABLE COMBUSTION POLYMERIC COMPOSITIONS
IT23844/81A IT1139954B (en) 1980-09-09 1981-09-08 HARDENABLE POLYMER COMPOSITIONS BY RADIATION THAT DELAY FLAME PROPAGATION
GB8127085A GB2083480B (en) 1980-09-09 1981-09-08 Flame retardant compositions
BE0/205902A BE890269A (en) 1980-09-09 1981-09-08 POLYMERIC DELAYING COMBUSTION COMPOSITIONS, CURABLE BY IRRADIATION
JP56140439A JPS5778438A (en) 1980-09-09 1981-09-08 Radiation-curable flame retardant polymer composition
CA000385534A CA1172784A (en) 1980-09-09 1981-09-09 Flame retardant radiation curable polymer compositions
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US4456654A (en) * 1982-05-24 1984-06-26 Eaton Corporation Electrical cable insulated with an elastomeric flame retardant composition
US4717742A (en) * 1985-05-29 1988-01-05 Beshay Alphons D Reinforced polymer composites with wood fibers grafted with silanes - grafting of celluloses or lignocelluloses with silanes to reinforce the polymer composites
US5059651A (en) * 1982-12-23 1991-10-22 Sumitomo Electric Industries, Ltd. Flame retardant and smoke suppressed polymeric composition and electric wire having sheath made from such composition
US5134175A (en) * 1987-12-16 1992-07-28 Michael Lucey Curable composition for electrical and electronic components
US5180757A (en) * 1987-12-16 1993-01-19 Michael Lucey Photopolymerizable compositions used in electronics
US5191004A (en) * 1991-03-22 1993-03-02 Quantum Chemical Corporation Flame retardant crosslinkable polymeric compositions having improved processability
US5218027A (en) * 1988-03-18 1993-06-08 Motrile Industries, Ltd. Low toxicity fire retardant thermoplastic material
US5225469A (en) * 1990-08-03 1993-07-06 Quantum Chemical Corporation Flame retardant polymeric compositions
US5306739A (en) * 1987-12-16 1994-04-26 Mlt/Micro-Lite Technology Corporation Highly filled polymeric compositions
US5401787A (en) * 1994-05-04 1995-03-28 Quantum Chemical Corporation Flame retardant insulation compositions
US5412012A (en) * 1994-01-24 1995-05-02 Quantum Chemical Corporation Flame retardant insulation compositions having improved strippability
US5439965A (en) * 1993-09-16 1995-08-08 Quantum Chemical Corporation Abrasion resistant crosslinkable insulation compositions
US5463653A (en) * 1993-04-30 1995-10-31 Cegelec Metals Systems Power converter device for direct current power supply to an electric arc furnace
EP0700962A1 (en) 1994-09-07 1996-03-13 Quantum Chemical Corporation Flame retardant insulation compositions having enhanced curability
US5573816A (en) * 1995-06-06 1996-11-12 Norton Company Friction coating for film backings
US5688851A (en) * 1995-09-18 1997-11-18 Ceramal Research & Development Corporation Gel coat and method for manufacture thereof
US5710202A (en) * 1996-01-05 1998-01-20 Kuckro; Gerard W. Flame retardant composition
US6096816A (en) * 1996-01-05 2000-08-01 Gerard Kuckro Flame retardant composition
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US6372828B2 (en) 1999-11-08 2002-04-16 Equistar Chemicals, Lp High temperature flame retardant insulation compositions stabilized with zinc salt/secondary amine combinations
US20040072930A1 (en) * 2002-10-10 2004-04-15 Lee Lester Y. Flame retardant insulation composition having improved scorch resistance
US6787694B1 (en) 2000-06-01 2004-09-07 Cable Design Technologies, Inc. Twisted pair cable with dual layer insulation having improved transmission characteristics
US20050058795A1 (en) * 2003-09-15 2005-03-17 Beck Harold D. Vinyl ester hose and method for manufacture of such hose
US20050059763A1 (en) * 2003-09-15 2005-03-17 Beck Harold D. Elastomer compositions for use in a hydrocarbon resistant hose
US20050065250A1 (en) * 2003-09-24 2005-03-24 Davis Donna Sue Inorganic antiblock
US20050121665A1 (en) * 2003-12-04 2005-06-09 Stijn Gillissen UV curable protective encapsulant
US20060263556A1 (en) * 2003-09-15 2006-11-23 Dayco Products, Llc Elastomer compositions for use in a hydrocarbon resistant hose
US20080134628A1 (en) * 2004-10-25 2008-06-12 Clement Hiel Fire-Protection Walls of Cementitious Composite Materials
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US4440907A (en) * 1981-08-20 1984-04-03 Union Carbide Corporation Process of producing a water-curable, silane modified alkylene-alkyl acrylate copolymer by reacting an alkylene-alkyl acrylate copolymer with a polysiloxane predispersed in a thermoplastic resin matrix
US4456654A (en) * 1982-05-24 1984-06-26 Eaton Corporation Electrical cable insulated with an elastomeric flame retardant composition
US5059651A (en) * 1982-12-23 1991-10-22 Sumitomo Electric Industries, Ltd. Flame retardant and smoke suppressed polymeric composition and electric wire having sheath made from such composition
US4717742A (en) * 1985-05-29 1988-01-05 Beshay Alphons D Reinforced polymer composites with wood fibers grafted with silanes - grafting of celluloses or lignocelluloses with silanes to reinforce the polymer composites
US5134175A (en) * 1987-12-16 1992-07-28 Michael Lucey Curable composition for electrical and electronic components
US5180757A (en) * 1987-12-16 1993-01-19 Michael Lucey Photopolymerizable compositions used in electronics
US5306739A (en) * 1987-12-16 1994-04-26 Mlt/Micro-Lite Technology Corporation Highly filled polymeric compositions
US5218027A (en) * 1988-03-18 1993-06-08 Motrile Industries, Ltd. Low toxicity fire retardant thermoplastic material
US5225469A (en) * 1990-08-03 1993-07-06 Quantum Chemical Corporation Flame retardant polymeric compositions
US5191004A (en) * 1991-03-22 1993-03-02 Quantum Chemical Corporation Flame retardant crosslinkable polymeric compositions having improved processability
US5463653A (en) * 1993-04-30 1995-10-31 Cegelec Metals Systems Power converter device for direct current power supply to an electric arc furnace
US5439965A (en) * 1993-09-16 1995-08-08 Quantum Chemical Corporation Abrasion resistant crosslinkable insulation compositions
US5412012A (en) * 1994-01-24 1995-05-02 Quantum Chemical Corporation Flame retardant insulation compositions having improved strippability
US5401787A (en) * 1994-05-04 1995-03-28 Quantum Chemical Corporation Flame retardant insulation compositions
EP0700962A1 (en) 1994-09-07 1996-03-13 Quantum Chemical Corporation Flame retardant insulation compositions having enhanced curability
US6197864B1 (en) 1994-09-07 2001-03-06 Equistar Chemicals, Lp Flame retardant insulation compositions having enhanced curability
US5573816A (en) * 1995-06-06 1996-11-12 Norton Company Friction coating for film backings
US5688851A (en) * 1995-09-18 1997-11-18 Ceramal Research & Development Corporation Gel coat and method for manufacture thereof
US6096816A (en) * 1996-01-05 2000-08-01 Gerard Kuckro Flame retardant composition
US5710202A (en) * 1996-01-05 1998-01-20 Kuckro; Gerard W. Flame retardant composition
US6372828B2 (en) 1999-11-08 2002-04-16 Equistar Chemicals, Lp High temperature flame retardant insulation compositions stabilized with zinc salt/secondary amine combinations
WO2001074936A1 (en) * 2000-04-03 2001-10-11 Equistar Chemicals, Lp Improved radiation curable wire and cable insulation compositions
US6326422B1 (en) 2000-04-03 2001-12-04 Equistar Chemicals, Lp Radiation curable wire and cable insulation compositions
US6787694B1 (en) 2000-06-01 2004-09-07 Cable Design Technologies, Inc. Twisted pair cable with dual layer insulation having improved transmission characteristics
US6984677B2 (en) 2002-10-10 2006-01-10 Equistar Chemicals, Lp Flame retardant insulation composition having improved scorch resistance
US20040072930A1 (en) * 2002-10-10 2004-04-15 Lee Lester Y. Flame retardant insulation composition having improved scorch resistance
US20050058795A1 (en) * 2003-09-15 2005-03-17 Beck Harold D. Vinyl ester hose and method for manufacture of such hose
US20050059763A1 (en) * 2003-09-15 2005-03-17 Beck Harold D. Elastomer compositions for use in a hydrocarbon resistant hose
US20060263556A1 (en) * 2003-09-15 2006-11-23 Dayco Products, Llc Elastomer compositions for use in a hydrocarbon resistant hose
US20050065250A1 (en) * 2003-09-24 2005-03-24 Davis Donna Sue Inorganic antiblock
US20050121665A1 (en) * 2003-12-04 2005-06-09 Stijn Gillissen UV curable protective encapsulant
US7479653B2 (en) 2003-12-04 2009-01-20 Henkel Ag & Co Kgaa UV curable protective encapsulant
US20080134628A1 (en) * 2004-10-25 2008-06-12 Clement Hiel Fire-Protection Walls of Cementitious Composite Materials
US7658042B2 (en) 2004-10-25 2010-02-09 Composite Support & Solutions, Inc. Fire-protection walls of cementitious composite materials
US9458326B2 (en) 2009-09-09 2016-10-04 Felix Winkelmann Polymer materials comprising coupled components
CN102627665A (en) * 2012-04-13 2012-08-08 阜新恒通氟化学有限公司 Perfluorohexylethyl-vinyl-dimethoxy silane and preparation method as well as application thereof
WO2018067721A1 (en) 2016-10-07 2018-04-12 Equistar Chemicals, Lp Silicone elastomer compositions, composite materials, and methods

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NO813049L (en) 1982-03-10
NL189303B (en) 1992-10-01
NO159533B (en) 1988-10-03
IE812050L (en) 1982-03-09
GB2083480A (en) 1982-03-24
MX157682A (en) 1988-12-09
FR2489831A1 (en) 1982-03-12
DE3135749C2 (en) 1991-05-08
DE3135749A1 (en) 1982-05-06
CA1172784A (en) 1984-08-14
NO159533C (en) 1989-01-11
JPH0222100B2 (en) 1990-05-17
GB2083480B (en) 1984-08-15
BE890269A (en) 1982-03-08
IE51546B1 (en) 1987-01-07
JPS5778438A (en) 1982-05-17
IT8123844A0 (en) 1981-09-08
IT1139954B (en) 1986-09-24
NL8104161A (en) 1982-04-01
NL189303C (en) 1993-03-01
FR2489831B1 (en) 1985-03-22
BR8105711A (en) 1982-05-25

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